WO2012164897A1 - 水素生成装置及びその運転方法並びに燃料電池システム - Google Patents
水素生成装置及びその運転方法並びに燃料電池システム Download PDFInfo
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0432—Temperature; Ambient temperature
- H01M8/04373—Temperature; Ambient temperature of auxiliary devices, e.g. reformers, compressors, burners
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- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0675—Removal of sulfur
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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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- C01B2203/1258—Pre-treatment of the feed
- C01B2203/1264—Catalytic pre-treatment of the feed
- C01B2203/127—Catalytic desulfurisation
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- C01B2203/14—Details of the flowsheet
- C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
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- C01B2203/16—Controlling the process
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a hydrogen generator, an operating method thereof, and a fuel cell system, and more particularly to a device including a desulfurizer for desulfurizing a raw material.
- the hydrogen generator is used, for example, to supply a hydrogen-containing gas as a fuel gas to a fuel cell.
- a hydrogen generator generally includes a reformer that generates a hydrogen-containing gas by a reforming reaction between a raw material and water. City gas or the like is used as the raw material, and these gases contain sulfur compounds as odorous components. Since this sulfur compound is a poisoning substance for the reforming catalyst used in the reforming reaction, it must be removed by some method.
- room temperature adsorptive desulfurization a method of removing by room temperature adsorption
- Patent Document 2 a method of removing hydrogen by hydrodesulfurization using hydrogen
- a hydrogen generator using hydrodesulfurization has been proposed (see, for example, Patent Document 2) after room temperature adsorptive desulfurization is used at start-up and hydrogen-containing gas can be generated.
- JP 2004-228016 A Japanese Patent Laid-Open No. 1-275697
- the present invention solves the above-mentioned problems, and a hydrogen generator and its operation in which the possibility that a problem occurs due to the adsorption of a sulfur compound not converted to hydrogen sulfide to a hydrodesulfurization catalyst is reduced as compared with the prior art. It is an object to provide a method and a fuel system.
- One aspect of the hydrogen generator of the present invention includes a reformer that generates a hydrogen-containing gas using a raw material, and a first desulfurizer that adsorbs and desulfurizes a sulfur compound contained in the raw material supplied to the reformer.
- a second desulfurizer that hydrodesulfurizes a sulfur compound contained in the raw material supplied to the reformer, and a raw material that passes through at least the first desulfurizer and is supplied to the reformer.
- a flow controller that selectively enables and blocks the flow of a hydrogen-containing gas from the upstream end to the downstream end of the Before the stop of the generation of the gas and at the time of starting, the switch is switched to the first path side while generating the hydrogen-containing gas in the reformer, and the hydrogen-containing gas is supplied to the flow controller.
- a controller configured to execute a process that enables distribution of the data.
- One aspect of the fuel cell system of the present invention includes the hydrogen generation device and a fuel cell that generates electric power using the hydrogen-containing gas supplied from the hydrogen generation device.
- the raw material that has passed through the first desulfurizer that removes sulfur compounds in the raw material is at least one of before and after the stop of the production of the hydrogen-containing gas.
- the step of supplying to the reformer and the step of supplying the hydrogen-containing gas generated in the reformer to a second desulfurizer that hydrodesulfurizes the sulfur compound in the raw material are both executed.
- a hydrogen generator, a method of operating the same, and a fuel system which are less likely to cause problems due to adsorption of a sulfur compound not converted to hydrogen sulfide to a hydrodesulfurization catalyst. Can be provided.
- FIG. 1 is a block diagram showing an example of the configuration of the hydrogen generator according to Embodiment 1.
- FIG. 2 is a flowchart showing an example of the processing operation of the hydrogenated sulfur compound of the hydrogen generator of FIG.
- FIG. 3 is a block diagram showing an example of the configuration of the hydrogen generator according to Modification 1 of Embodiment 1.
- FIG. 4 is a block diagram showing an example of the configuration of the hydrogen generator according to Embodiment 2.
- FIG. 5 is a flowchart showing an example of the processing operation of the hydrogenated sulfur compound of the hydrogen generator according to Embodiment 2.
- FIG. 6 is a block diagram showing a configuration in which the open valve 8 is replaced with another example of the flow controller in the hydrogen generator of the first embodiment as the hydrogen generator according to the fourth embodiment.
- FIG. 7 is a block diagram showing a configuration in which the open valve 8 is replaced with another example of the flow controller in the hydrogen generator of the first modification of the first embodiment as the hydrogen generator according to the fourth embodiment.
- FIG. 8 is a block diagram showing a configuration in which the open valve 8 is replaced with still another example of the flow controller in the hydrogen generator of Embodiment 1 as a hydrogen generator according to Embodiment 5.
- FIG. 9 is a block diagram showing a configuration in which the open valve 8 is replaced with still another example of the flow controller in the hydrogen generator of Modification 1 of Embodiment 1 as a hydrogen generator according to Embodiment 5.
- FIG. 10 is a block diagram showing an example of the configuration of the hydrogen generator according to Embodiment 6.
- FIG. 11 is a block diagram showing an example of the operation of the hydrogen generator according to Embodiment 6.
- FIG. 12 is a block diagram showing an example of the configuration of the fuel cell system according to Embodiment 7. In FIG.
- the hydrodesulfurization catalyst is configured such that the CoMo catalyst and the ZnO catalyst are sequentially arranged in the raw material flow, the unhydrogenated sulfur compound desorbed from the CoMo catalyst is not adsorbed by the ZnO catalyst, It flows into the reforming catalyst. For this reason, the reforming catalyst deteriorates.
- the hydrodesulfurization catalyst is configured such that the CoMo catalyst and the CuZnO catalyst are arranged in this order in the raw material flow, the unhydrogenated sulfur compound desorbed from the CoMo catalyst is adsorbed by CuZnO.
- this adsorption requires an increase in the capacity of the CuZnO catalyst.
- an increase in the size and cost of the desulfurizer occurs.
- the desulfurization performance decreases as the amount of the unhydrogenated sulfur compound adsorbed on the surface of CuZnO increases.
- the present invention has been made based on such knowledge.
- the hydrogen generator according to Embodiment 1 includes a reformer that generates a hydrogen-containing gas using a raw material, and a first desulfurizer that adsorbs and desulfurizes a sulfur compound contained in the raw material supplied to the reformer.
- a second desulfurizer that hydrodesulfurizes a sulfur compound contained in the raw material supplied to the reformer, and a raw material that passes through at least the first desulfurizer and is supplied to the reformer.
- a flow controller that selectively enables and blocks the flow of a hydrogen-containing gas from the upstream end to the downstream end of the Before the stop of the generation of the gas and at the time of starting, the switch is switched to the first path side while generating the hydrogen-containing gas in the reformer, and the hydrogen-containing gas is supplied to the flow controller.
- a controller configured to execute a process that enables distribution of the data.
- Such a configuration reduces the possibility of problems caused by the adsorption of sulfur compounds that are not converted to hydrogen sulfide to the hydrodesulfurization catalyst.
- the second desulfurizer may include a CoMo-based catalyst.
- the second desulfurizer may include a CuZn-based catalyst.
- the operation method of the hydrogen generator according to Embodiment 1 is the raw material that has passed through the first desulfurizer that removes sulfur compounds in the raw material at least one of before and after the start of generation of the hydrogen-containing gas. And a step of supplying the hydrogen-containing gas generated in the reformer to a second desulfurizer that hydrodesulfurizes the sulfur compound in the raw material.
- Such a configuration reduces the possibility of problems caused by the adsorption of sulfur compounds that are not converted to hydrogen sulfide to the hydrodesulfurization catalyst.
- FIG. 1 is a block diagram showing an example of the configuration of the hydrogen generator according to Embodiment 1.
- the hydrogen generator of Embodiment 1 includes a reformer 1, a first desulfurizer 2, a second desulfurizer 3, a branch path 4, a raw material flow path 5, and a switching.
- the reformer 1 generates a hydrogen-containing gas using raw materials.
- the reformer 1 includes a reforming catalyst (not shown), and the reforming catalyst uses the raw material and steam to advance a steam reforming reaction to generate a hydrogen-containing gas.
- the reforming catalyst for example, a Ru catalyst or a Ni catalyst is used.
- the generated hydrogen-containing gas is sent out from the outlet of the reformer 1.
- the raw material is supplied to the reformer 1 through a raw material supply path described later.
- the steam is supplied to the reformer 1 through a water supply path (not shown).
- the reformer 1 is heated to a predetermined temperature (for example, 650 ° C.) by a heater (not shown) and supplied with heat necessary for the steam reforming reaction.
- a reformer for reducing carbon monoxide in the hydrogen-containing gas produced by the reformer 1 by a shift reaction downstream of the reformer 1 and oxidizing the carbon monoxide in the hydrogen-containing gas.
- You may provide at least any one with the CO removal device (not shown) reduced by at least any one of reaction and methanation reaction.
- the reforming reaction that proceeds in the reformer 1 is not limited to the steam reforming reaction, and any reforming reaction may be used as long as it is a reforming reaction that generates a hydrogen-containing gas using raw materials. Absent. For example, it may be a partial oxidation reaction or an autothermal reaction.
- the downstream end of the raw material supply path is connected to the inlet of the reformer 1.
- the upstream end of the raw material supply path is connected to a raw material supply source (not shown).
- the raw material is a gas containing an organic compound having at least hydrogen and carbon as constituent elements. Examples of the raw material include hydrocarbon gas such as city gas mainly composed of methane, natural gas, and LPG.
- the raw material contains a sulfur compound as an odorant component or derived from the raw material.
- Examples of the raw material supply source include a raw material infrastructure, a cylinder for storing the raw material, and the like.
- This raw material supply path includes a branch path 4, a raw material flow path 5, and a switch 6. The raw material from the raw material supply source is supplied to the switch 6.
- the switch 6 switches the supply destination of the supplied raw material between the branch path 4 and the raw material flow path 5.
- the switch 6 is configured by, for example, a three-way valve, or an open / close valve provided in each of the branch path 4 and the raw material flow path 5.
- the branch path 4 and the raw material flow path 5 merge at a junction 11.
- the first desulfurizer 2 is provided in the branch path 4.
- the first desulfurizer 2 removes sulfur compounds in the raw material by physical adsorption desulfurization at room temperature.
- “normal temperature” means a temperature that is relatively close to the normal temperature range compared to the operating temperature of the hydrodesulfurization catalyst (usually around 300 ° C.). From the normal temperature range, the first desulfurizer 2 is used. Up to a temperature at which the desulfurizing agent used effectively functions.
- the desulfurization agent include zeolite adsorbents obtained by ion exchange of Ag for removing odor components, activated carbon, and the like.
- the raw material flow path 5 is a flow path through which only the second desulfurizer 3 out of the first desulfurizer 2 and the second desulfurizer 3 passes and the raw material supplied to the reformer 1 flows.
- the raw material flow path 5 bypasses the first desulfurizer 2, passes only through the second desulfurizer 3, and is connected to the reformer 1.
- the raw material supplier 9 adjusts the flow rate of the raw material supplied to the reformer 1.
- the raw material supplier 9 includes, for example, a booster such as a booster pump and a flow rate adjustment valve, but is not limited thereto, and may be either a booster or a flow rate adjustment valve.
- the second desulfurizer 3 hydrodesulfurizes sulfur compounds in the raw material.
- the hydrodesulfurization catalyst include first to third hydrodesulfurization catalysts.
- the first hydrodesulfurization catalyst is configured such that a CoMo catalyst and a ZnO catalyst are sequentially arranged in the raw material flow.
- the second hydrodesulfurization catalyst is configured such that a CoMo-based catalyst and a CuZnO catalyst are sequentially arranged in the raw material flow.
- the third hydrodesulfurization catalyst is configured to include a CuZn-based catalyst.
- the CoMo-based catalyst converts the sulfur compound in the raw material into hydrogen sulfide.
- the converted hydrogen sulfide is chemisorbed by the ZnO catalyst.
- the CoMo catalyst converts the sulfur compound in the raw material into hydrogen sulfide.
- the CuZnO catalyst chemisorbs the converted hydrogen sulfide.
- the second hydrogenation catalyst may include both a ZnO-based catalyst and a CuZn-based catalyst as hydrogen sulfide chemical adsorbents. Any of the ZnO-based catalyst and the CuZn-based catalyst may be disposed upstream.
- the CuZn-based catalyst converts the sulfur compound in the raw material into hydrogen sulfide, and the converted hydrogen sulfide is adsorbed by the CuZn-based catalyst. Further, the CuZn-based catalyst can also adsorb sulfur compounds in the raw material that are not converted to hydrogen sulfide.
- the second desulfurizer 3 is subjected to hydrodesulfurization at a predetermined temperature higher than room temperature (for example, 300 to 400 ° C.).
- the predetermined temperature is set so as to include at least a part of the use temperature of the hydrodesulfurization catalyst.
- the use temperature is a temperature suitable for use of the hydrodesulfurization catalyst and is a temperature at which the desulfurization performance is appropriately exhibited.
- the second desulfurizer 3 is installed in the vicinity of the reformer 1 and is configured to be heated by heat transmitted from the reformer 1.
- the second desulfurizer 3 may be heated by a heat source independent of the reformer 1 such as an electric heater, or may be configured to transfer heat from at least one of a transformer and a CO remover (not shown). Absent.
- the hydrogen generator of Embodiment 1 includes a first path 31 through which at least the first desulfurizer 2 passes and the raw material is supplied to the reformer 1, and the first desulfurizer and the second desulfurizer. And a second path 32 through which only the second desulfurizer passes and the raw material is supplied to the reformer.
- the second path 32 is composed of the raw material flow path 5.
- the first path 31 includes the branch path 4 and the raw material flow path 5 downstream from the junction 11.
- the first path 31 is configured to pass through the first desulfurizer 2 and the second desulfurizer 3 and to supply the raw material to the reformer 1.
- route 31 should just be comprised so that it may pass at least the 1st desulfurizer 2, and is not limited to this example.
- Other forms of the first path 31 will be described in detail in Modification 1 of Embodiment 1 described later.
- the switch 6 plays a role of switching the supply path of the raw material to the reformer 1 between the first path 31 and the second path 32.
- the hydrogen generator of Embodiment 1 includes a third path for supplying the hydrogen-containing gas generated in the reformer 1 to the second desulfurizer 3.
- the third path is constituted by the recycle channel 7.
- the recycle channel 7 is provided with an on-off valve 8 as an example of a flow controller.
- the flow controller is not limited to this example as long as it has a function of selectively enabling and blocking the flow of the hydrogen-containing gas from the upstream end to the downstream end of the recycle channel 7. Another example of the distribution controller will be described in Embodiment 3-6.
- downstream end of the recycling flow path 7 is joined to the raw material flow path 5 between the raw material feeder 9 and the junction 11.
- the upstream end of the recycle channel 7 is connected to a gas channel downstream of the reformer 1.
- the upstream end of the recycle flow path 7 is a gas flow path downstream from the reformer 1, You can connect.
- the upstream end of the recycle channel 7 may be connected to, for example, a gas channel between the reformer 1 and the downstream reactor, or may be connected to a gas channel downstream of the transformer. , It may be connected to a gas flow path downstream of the CO remover.
- a condenser (not shown) for lowering the dew point of the recycled gas may be provided in the recycling flow path 7.
- downstream end of the recycling flow path 7 is not limited to the above example, and may be connected to any location as long as it is a path upstream from the second desulfurizer 3.
- the upstream path from the second desulfurizer 3 is either the first path 31 or the second path 32.
- the downstream end of the recycling flow path 7 is connected to a path upstream of the second desulfurizer 3 and downstream of the raw material supply device 9 (raw material flow path 5).
- the recycling flow path 7 is appropriately connected.
- a booster may be provided.
- the controller 12 controls the switch 6 and the distribution controller. Specifically, the controller 12 generates the hydrogen-containing gas in the reformer 1 at least one of before the start of the generation of the hydrogen-containing gas and at the start-up, and switches the switch 6 to the first path 31 side. And a process for enabling the flow controller to flow the hydrogen-containing gas.
- the controller 12 only needs to have a control function, and includes an arithmetic processing unit (not shown) and a storage unit (not shown) that stores a control program. Examples of the arithmetic processing unit include an MPU and a CPU. A memory is exemplified as the storage unit.
- the controller 12 means not only a single controller but also a controller group controlled by a plurality of controllers in cooperation. The controller 12 performs later-described control by the arithmetic processing unit reading and executing the control program stored in the storage unit.
- FIG. 2 is a flowchart showing an example of the operation of the hydrogen generator of FIG.
- the controller 12 generates the hydrogen-containing gas in the reformer 1 (step S ⁇ b> 1) before at least one of the stop of the generation of the hydrogen-containing gas and at the time of start-up.
- a process of switching to the first path 31 side and allowing the flow controller to flow the hydrogen-containing gas from the upstream end to the downstream end of the recycle channel 7 is executed (steps S2 and S3).
- the flow of the hydrogen-containing gas is made possible by opening the on-off valve 8 which is a flow controller.
- production stop of the hydrogen-containing gas means that the supply of the raw material to the reformer 1 is stopped during the generation of the hydrogen-containing gas. Normally, when the hydrogen generator is stopped, the controller 12 controls the raw material supplier 9 and the supply of the raw material to the reformer 1 is stopped.
- steps S1-S3 are executed together, the order in which steps S1-S3 are started is arbitrary. That is, all three steps may be started at the same time, or the start timing of one to three steps may be different. In the latter case, the three steps S1-S3 may be started in any order.
- ⁇ Operation example 1> In the first operation example, the following process is executed when the hydrogen generator is stopped. Specifically, in the reformer 1, when the hydrogen-containing gas is generated, the switch 6 is switched to the second path 32 side, and the on-off valve 8 serving as a flow controller is opened so that the hydrogen-containing gas flows. It is possible. That is, the raw material supplied to the reformer 1 flows bypassing the first desulfurizer 2, and a part of the hydrogen-containing gas generated in the reformer 1 is added to the reformer 1 through the recycle channel 7. Is done. The raw material to which the hydrogen-containing gas is added is supplied to the second desulfurizer 3, where it is hydrodesulfurized and supplied to the reformer 1.
- the controller 12 controls the raw material supplier 9 to continue the supply of the raw material to the reformer 1 to generate a hydrogen-containing gas in the reformer 1 and open and close it.
- a process of switching the switch 6 from the second path 32 side to the first path 31 side is performed in a state where the valve 8 is opened to allow the hydrogen-containing gas to flow.
- “when the hydrogen generator is stopped” means when the generation of hydrogen-containing gas in the reformer 1 is stopped. Specifically, when the scheduled stop time of the hydrogen generator is approaching, or when a stop command for the hydrogen generator is input by an operator via an operating device (for example, a remote controller).
- an operating device for example, a remote controller
- the supply of the raw material to the reformer 1 by the raw material supplier 9 is stopped and the on-off valve 8 which is a flow controller is closed to prevent the hydrogen-containing gas from flowing, and the hydrogen generator is stopped. That is, before the hydrogen-containing gas production is stopped in the reformer 1, in other words, the processing is executed prior to the hydrogen-containing gas production stop.
- the switch 6 is maintained on the second path 32 side until the supply of the raw material to the reformer 1 is stopped when the hydrogen-containing gas is generated.
- the hydrogen-containing gas supplied to the second desulfurizer 3 is consumed in the hydrogenation reaction of the sulfur compound contained in the undesulfurized raw material gas newly supplied to the second desulfurizer 3.
- the hydrogen generator stops while the unhydrogenated sulfur compound adhering to the hydrodesulfurization catalyst of the second desulfurizer 3 remains.
- a problem may occur when the raw material is supplied to the second desulfurizer 3 at the next startup of the hydrogen generator.
- the subsequent hydrogen sulfide absorbent is a ZnO-based catalyst, such as the first hydrodesulfurization catalyst
- the desorbed sulfur compound is not hydrogen sulfide, so the removal is not possible with this ZnO-based catalyst. Instead, it flows into the reforming catalyst.
- the subsequent hydrogen sulfide absorbent is a CuZn-based catalyst as in the case of the second hydrodesulfurization catalyst
- the dehydrogenated unhydrogenated sulfur compound is physically adsorbed.
- the adsorption removal of hydrogen sulfide which is chemical adsorption
- the adsorption removal of the unhydrogenated sulfur compound which is physical adsorption
- the CuZn-based catalyst is desorbed from the CoMo-based catalyst. If an attempt is made to secure an adsorption capacity for the unhydrogenated sulfur compound, the size and cost of the second desulfurizer will be increased.
- the hydrodesulfurization catalyst is the third hydrodesulfurization catalyst, the desulfurization performance decreases due to an increase in the amount of the unhydrogenated sulfur compound adsorbed on the surface of CuZnO. Catalyst sulfur poisoning proceeds.
- the hydrogen generator of this embodiment has a problem when the unhydrogenated sulfur compound remaining on the hydrodesulfurization catalyst of the second desulfurizer 3 is supplied to the reformer together with the raw material at the time of startup. The possibility is reduced over conventional hydrogen generators.
- the hydrogen generator executes the following process at the time of startup. Specifically, the controller 12 raises the temperature of the reformer 1 and the second desulfurizer 3 at the time of startup. When the reformer 1 reaches a temperature at which the hydrogen-containing gas can be generated, the controller 12 supplies steam to the reformer 1 and controls the raw material supplier 9 to supply the raw material to the reformer 1, thereby containing hydrogen. Start gas production.
- the on-off valve 8 which is a flow controller is opened to allow the flow of the hydrogen-containing gas and the switch 6 is set to the first desulfurizer 3. Switch to the path 31 side.
- controller 12 switches the switch 6 to the second path 32 side.
- the controller 12 operates the hydrogen generator as in the operation example 2 when starting the hydrogen generator, and when the hydrogen generator operates and stops the hydrogen generator as in the operation example 1. Operate the generator. As a result, the possibility of problems due to the unhydrogenated sulfur compound remaining on the hydrodesulfurization catalyst of the second desulfurizer 3 is reduced as compared with the prior art.
- FIG. 3 is a block diagram showing an example of the configuration of the hydrogen generator according to Modification 1 of Embodiment 1.
- the first path 31 is configured such that the raw material passes through only the first desulfurizer 2 and is supplied to the reformer 1.
- Other configurations are the same as those of the first embodiment (configuration of FIG. 1).
- the downstream end of the branch path 4 joins at the junction point 11 in the raw material flow path 5 downstream from the second desulfurizer 3.
- the other components denoted by the same reference numerals as those in FIG. 1 are the same as those in the first embodiment, and thus detailed description thereof is omitted.
- the controller 6 switches the switch 6 to the first path 31 side while generating the hydrogen-containing gas in the reformer 1 when the controller 12 stops and / or starts up the hydrogen generator.
- the processing for opening the on-off valve 8 which is a flow controller and enabling the flow of the hydrogen-containing gas is executed, the raw material desulfurized by the first desulfurizer 2 is supplied to the reformer 1 by the raw material supplier 9.
- the hydrogen-containing gas generated in the reformer 1 is supplied to the second desulfurizer 3 via the recycle channel 7.
- Such a configuration makes it possible to shorten the period for executing the above-described processing at least one of before the stop of the generation of the hydrogen-containing gas and at the start-up, as compared with the hydrogen generator of Embodiment 1.
- the timing for starting the measurement of the operation time is arbitrarily set.
- the time for starting the supply of the raw material to the second desulfurizer 3, the time for starting the production of the hydrogen-containing gas in the reformer 1, and the like may be used as the timing for starting the measurement of the operation time.
- the first time threshold is a time when it is determined that the above process needs to be executed, and the value is arbitrarily set. For example, as will be described later, when the hydrogen generator is incorporated in a fuel cell system and used, the first time threshold is set to 24 hours from the start of power generation (activation of the hydrogen generator). Note that the first time threshold may be changed according to the power generation performance of each consumer who uses the fuel cell system.
- the hydrogen generator of Modification 3 is the hydrogen generator of Modification 2, and the first time threshold value is set according to the cumulative raw material supply amount to the second desulfurizer. With such a configuration, it is possible to shorten the period for executing the above-described processing at least one of before the stop of the generation of the hydrogen-containing gas and at the start-up, as compared with the first embodiment.
- Modification 4 The hydrogen generator of Modification 4 is the same as that of Embodiment 1 or Modification 1-3, in which the controller switches while generating the hydrogen-containing gas in the reformer for a predetermined time or longer.
- the apparatus is configured to execute a process of switching the vessel to the first path side and allowing the flow controller to flow the hydrogen-containing gas.
- the hydrogen-containing gas generated in the reformer is supplied to the second desulfurizer to hydrogenate the unhydrogenated sulfur compound adhering to the hydrodesulfurization catalyst of the second desulfurizer.
- the “predetermined time” may be set in accordance with, for example, the cumulative amount of raw material supplied to the second desulfurizer.
- the unhydrogenated sulfur compound attached to the hydrodesulfurization catalyst of the second desulfurizer can be appropriately hydrogenated and removed from the unhydrogenated sulfur compound.
- Modification 5 The hydrogen generator of Modification 5 is the same as that of Embodiment 1 or Modification 1-4, in which the controller is configured such that the temperature of the hydrodesulfurization catalyst provided in the second desulfurizer is It may be configured to switch the switch to the second path side when it is at the operating temperature.
- the hydrogen generator of the present modification is configured in the same manner as the hydrogen generator of Embodiment 1 shown in FIG. 1, detailed description thereof is omitted.
- the controller 12 switches the switch 6 to the second path 32 side when the temperature of the hydrodesulfurization catalyst provided in the second desulfurizer 3 is the operating temperature. It is configured. At this time, the on-off valve 8 is opened so as to allow the hydrogen-containing gas to flow from the upstream end to the downstream end of the recycle channel 7.
- Step 3 shown in FIG. 2 is executed to switch the switch 6 to the first path 31 side, and after maintaining the open state of the on-off valve 8, the switch 6 is switched to the second path 32 side.
- the timing is arbitrary.
- the temperature of the second desulfurizer may be switched to the second path 32 side when the temperature is the use temperature, or may be switched to the second path 32 side when the temperature is lower than the use temperature. Good.
- Embodiment 2 The hydrogen generator of Embodiment 2 is the same as that of Embodiment 1 or Modification 1-5, and the controller is provided in the second desulfurizer in the above-described processing at the time of startup. When the temperature of the hydrodesulfurization catalyst is lower than the operating temperature, the flow controller is controlled to start the flow of the hydrogen-containing gas.
- the hydrogen generator of the present embodiment may be configured in the same manner as the hydrogen generator of any one of Embodiment 1 and Modifications 1-5, except for the above features.
- FIG. 4 is a block diagram showing an example of the configuration of the hydrogen generator according to Embodiment 2.
- the temperature of the hydrodesulfurization catalyst provided in the second desulfurizer 3 is lower than the operating temperature, as described above.
- the hydrogen-containing gas is circulated by opening the on-off valve 8 which is an example of a flow controller while generating the hydrogen-containing gas in the reformer 1 while the switch 6 is switched to the first path 31 side.
- the said temperature lower than the use temperature of the hydrodesulfurization catalyst provided in the 2nd desulfurizer 3 is set arbitrarily.
- the use temperature of the hydrodesulfurization catalyst is a temperature suitable for use, and usually the hydrodesulfurization reaction proceeds even at a temperature lower than the use temperature.
- the other configuration is the same as that of the operation example 2 of the hydrogen generator of the first embodiment.
- the hydrogen generator of this embodiment includes a detector that detects the temperature of the hydrodesulfurization catalyst provided in the second desulfurizer 3, and this detector is the temperature of the second desulfurizer 3. May be detected directly or indirectly. “Detecting directly” means detecting the temperature of the hydrodesulfurization catalyst provided in the second desulfurizer 3 itself. “Detecting indirectly” means detecting a physical quantity (parameter) having a correlation with the temperature of the hydrodesulfurization catalyst provided in the second desulfurizer 3.
- the temperature detector 13 for detecting the temperature of the hydrodesulfurization catalyst provided in the second desulfurizer 3 is provided, and the water provided in the second desulfurizer 3 is provided.
- the temperature of the hydrodesulfurization catalyst is directly detected.
- Examples of the temperature detector 13 include temperature sensors such as thermocouples and thermistors.
- the detector that detects the temperature of the hydrodesulfurization catalyst is the temperature of the reformer 1. It may be a temperature detector that detects.
- the temperature of the second desulfurizer 3 is indirectly detected at the detected temperature of the reformer 1 detected by the temperature detector.
- the detector that detects the temperature of the second desulfurizer 3 may be a timer that detects an elapsed time since the start of the hydrogen generator.
- the temperature of the second desulfurizer 3 is indirectly detected at the elapsed time measured by the timer.
- the hydrodesulfurization catalyst is a catalyst from which the unhydrogenated sulfur compound is desorbed when gas is flowed at a temperature lower than the operating temperature
- the unhydrogenated sulfur attached on the hydrodesulfurization catalyst of the second desulfurizer 3 The flow of the hydrogen-containing gas may be started by controlling the flow controller (in this example, the on-off valve 8) below the upper limit temperature at which the compound does not desorb.
- the temperature threshold value of the second desulfurizer that starts the flow of the hydrogen-containing gas by controlling the flow controller is equal to or lower than the use temperature, and the non-water adhering to the hydrodesulfurization catalyst of the second desulfurizer 3 Any temperature may be used as long as the sulfur compound is hydrogenated. Such a temperature threshold value can be obtained by experiments or the like.
- the second desulfurizer 3 may be configured to control the temperature independently of the reformer 1.
- the second desulfurizer 3 may be configured to be heated by a heater separate from the reformer 1 such as an electric heater.
- the second desulfurizer 3 may be configured to be heated by heat transmitted from the reformer 1 and to adjust the amount of heat transmitted.
- the controller 12 controls the temperature of the second desulfurizer 3 by controlling the heating amount for the second desulfurizer 3.
- FIG. 5 is a flowchart showing an example of the processing operation of the hydrogen generator of the third embodiment.
- the controller 12 in the second embodiment, the controller 12 is in a state where the temperature of the hydrodesulfurization catalyst provided in the second desulfurizer 3 is equal to or lower than the operating temperature when the hydrogen generator is started.
- the switch 6 is switched to the first path 31 side and the reformer 1 generates a hydrogen-containing gas (step S11). Specifically, the controller 12 raises the temperature of the reformer 1 and the second desulfurizer 3 at the time of startup.
- the switcher 6 switches to the first path 31 side, and the raw material that has passed through the first desulfurizer 2 is supplied to the reformer 1, and hydrogen A contained gas is produced.
- the controller 12 determines whether or not the detected temperature detected by the temperature detector 13 is equal to or higher than the temperature threshold T1 (step S12). If the detected temperature is equal to or higher than T1 (Yes in step S12), the controller 12 The flow controller (open / close valve 8) is controlled so that the contained gas can flow (step S13). As a result, the hydrogen-containing gas is supplied to the second desulfurizer 3 via the recycle channel 7.
- the temperature threshold T1 is defined as a temperature at which the hydrodesulfurization reaction proceeds at a temperature lower than the use temperature.
- Embodiment 3 The hydrogen generator of Embodiment 3 is the same as the hydrogen generator of Embodiment 1, Modification 1-5, or Embodiment 2, but the second desulfurizer supplies the raw material at a temperature lower than the operating temperature. Then, a hydrodesulfurization catalyst from which the unhydrogenated sulfur compound is desorbed is provided, and the controller is a flow controller at a temperature lower than an upper limit temperature at which the unhydrogenated sulfur compound is not desorbed from the hydrodesulfurization catalyst in the processing at the time of startup. May be configured to allow the hydrogen-containing gas to flow.
- the upper limit temperature is desirably 150 ° C.
- the hydrogen generator of the present embodiment may be configured in the same manner as the hydrogen generator of any of Embodiment 1, Modification 1-5, or Embodiment 2 except for the above features.
- the second desulfurizer 3 includes a hydrodesulfurization catalyst from which unhydrogenated sulfur compounds are desorbed when a raw material is supplied at a temperature lower than the operating temperature.
- the controller 12 is configured such that the temperature of the hydrodesulfurization catalyst provided in the second desulfurizer 3 is the upper limit temperature at which the unhydrogenated sulfur compound is not desorbed from the hydrodesulfurization catalyst.
- the reformer 1 In the state where the switcher 6 is switched to the first path 31 side, the reformer 1 generates a hydrogen-containing gas while opening the on-off valve 8 which is an example of a flow controller when the switcher 6 is switched to the first path 31 side. Circulate gas.
- the upper limit temperature is 150 ° C.
- the upper limit temperature varies depending on the type of hydrodesulfurization catalyst.
- the temperature threshold value below the upper limit temperature at which the flow controller is controlled to start the flow of the hydrogen-containing gas is equal to or lower than the use temperature and is not adhered to the hydrodesulfurization catalyst of the second desulfurizer 3. Any temperature may be used as long as the hydrogenated sulfur compound is hydrogenated. Such a temperature threshold value can be obtained by experiments or the like. Thereafter, the switch 6 is switched to the second path 32 side and the temperature of the second desulfurizer 3 is increased.
- the other configuration is the same as that of the operation example 2 of the hydrogen generator of the first embodiment.
- the processing operation of the hydrogen generator of Embodiment 3 is the same as the processing operation of Embodiment 2 described above, except that the temperature threshold T1 is a temperature lower than the upper limit temperature instead of the temperature lower than the operating temperature.
- the other operations are the same as those in the second embodiment.
- the temperature threshold T1 is preferably a temperature at which the hydrodesulfurization reaction proceeds.
- Example 1 As an example of Embodiment 1, Embodiment 2 and Embodiment 3, a fixed bed flow reactor equipped with an electric furnace is provided with 10 cc of a CoMo catalyst and 5 cc of a ZnO catalyst as a hydrodesulfurization catalyst, and hydrogen Experiments were performed to simulate the behavior of the generator when it was stopped and restarted. That is, the case where the hydrodesulfurization catalyst was the first hydrodesulfurization catalyst was simulated.
- the fixed bed flow reaction apparatus was supplied with 13 cc (hereinafter referred to as desulfurization 13A) in which the sulfur component was adsorbed and removed with a zeolite-based adsorptive desulfurization agent as a raw material at 50 cc / min. TBM) at 10 ppm and hydrogen at 5 vol. % Was added.
- desulfurization 13A 13 cc in which the sulfur component was adsorbed and removed with a zeolite-based adsorptive desulfurization agent as a raw material at 50 cc / min. TBM) at 10 ppm and hydrogen at 5 vol. % Was added.
- hydrodesulfurization was performed at 300 to 400 ° C. while supplying the raw material to which the sulfur component and hydrogen were added to the fixed bed flow reactor.
- the supply of the sulfur component and the hydrogen-added raw material to the fixed bed flow reactor was continued for 450 hours, the supply of TBM and hydrogen was stopped simultaneously, and the temperature of the fixed bed flow reactor was lowered by cooling the electric furnace ( Simulating the stop operation in the operation example 2 of the first embodiment). Thereafter, the temperature of the electric furnace was raised while supplying the desulfurized 13A to the fixed bed flow reactor and the temperature of the fixed bed flow reactor was raised again (simulating the start-up operation in the first operation example of Embodiment 1).
- the supply of hydrogen was stopped, and then the temperature of the fixed bed flow reactor was lowered by cooling the electric furnace, and then the supply of desulfurization 13A was stopped (the embodiment).
- the stop operation in the first operation example 1 is simulated). After that, while supplying desulfurized 13A to the fixed bed flow reactor, the temperature of the electric furnace was raised and the temperature of the fixed bed flow reactor was raised again (simulating the start-up operation in the operation example 1 of Embodiment 1).
- the sulfur component (TBM) in the gas that passed through the desulfurization catalyst was below the detection limit (5 ppb).
- the sulfur component (TBM) in the gas that passed through the hydrodesulfurization catalyst was below the detection limit (5 ppb). That is, the temperature of the hydrodesulfurization catalyst was 150 ° C. or higher, and no desorption of sulfur components from the hydrodesulfurization catalyst was observed.
- the sulfur component (TBM) is estimated to be below the detection limit at the time of reheating. Further, this experiment simulates the operation example 3 of the first embodiment as a whole.
- this example supports the effect of reducing the problems caused by the unhydrogenated sulfur compound adhering to the hydrodesulfurization catalyst in each of the above-described embodiments and modifications as compared with the conventional example. It was.
- the hydrodesulfurization catalyst is a catalyst from which the unhydrogenated sulfur compound is desorbed when gas is supplied at a temperature lower than the use temperature
- the second desulfurizer 3 contains hydrogen at a temperature not higher than the upper limit temperature (150 ° C.). It was confirmed that the dehydrogenation of the unhydrogenated sulfur compound from the catalyst does not occur when the gas is supplied.
- route 31 side at the temperature higher than upper limit temperature (150 degreeC) after that, it is not water
- the added sulfur compound is hydrogenated to hydrogen sulfide, and the hydrogen sulfide is adsorbed. Therefore, even in such a case, it is clear that the problem caused by the unhydrogenated sulfur compound is reduced as compared with the conventional hydrogen generator.
- Example 2 As an example of Embodiment 1, Embodiment 2 and Embodiment 3, 500 cc of CuZnO-based catalyst was installed as a hydrodesulfurization catalyst in a fixed bed flow reactor equipped with an electric furnace, and the hydrogen generator was stopped and An experiment simulating the behavior at restart was performed. That is, the case where the hydrodesulfurization catalyst is the third hydrodesulfurization catalyst was simulated.
- desulfurization 13A obtained by adsorbing and removing a sulfur component with a zeolite-based adsorptive desulfurization agent as a raw material was supplied to the fixed bed flow reactor at 3 L / min, and tertiary butyl mercaptan as a sulfur component ( DMS) 500 ppm and hydrogen 5 vol. % was added.
- hydrodesulfurization was performed at 300 to 400 ° C. while supplying the raw material to which the sulfur component and hydrogen were added to the fixed bed flow reactor.
- Supply of the raw material to which the sulfur component and hydrogen were added to the fixed bed flow reactor was continued for 81 hours, and then the supply of DMS and hydrogen was stopped simultaneously.
- the sulfur component (DMS) in the gas after passing through the hydrodesulfurization catalyst was not more than the initial detection limit (5 ppb), but the raw material was supplied to the fixed bed flow reactor, and after 81 hours, Sulfur component (DMS) was detected at 300 ppb.
- the temperature of the electric furnace was lowered, and the temperature of the fixed bed flow reactor was lowered (simulating the stopping operation in the operation example 2 of the first embodiment).
- the temperature of the electric furnace is increased to reheat the fixed bed flow reactor, and hydrogen is added to the desulfurization 13A when 130 ° C. is reached (the embodiment).
- the start-up operation in the operation example 1 and the processing in the second embodiment are simulated).
- the sulfur component (DMS) in the gas when the hydrodesulfurization catalyst reached the operating temperature (250 ° C. in this example) was below the detection limit (5 ppb).
- the sulfur component (DMS) in the gas that passed through the hydrodesulfurization catalyst was below the detection limit (5 ppb).
- the sulfur component (DMS) is estimated to be below the detection limit at the time of reheating. Further, this experiment simulates the operation example 3 of the first embodiment as a whole.
- the fourth embodiment shows another example of the distribution controller.
- FIG. 6 is a block diagram showing a configuration in which the open valve 8 is replaced with another example of the flow controller in the hydrogen generator of the first embodiment as the hydrogen generator of the fourth embodiment.
- FIG. 7 is a block diagram showing a configuration in which the open valve 8 is replaced with another example of the flow controller in the hydrogen generator of the first modification of the first embodiment as the hydrogen generator according to the fourth embodiment.
- a predetermined pressure loss mechanism (flow path resistance) 42 is provided to the recycle flow path 7.
- the pressure loss mechanism 42 is applied, for example, by providing an orifice having a predetermined pressure loss (flow rate) or by designing the pipe diameter of the recycle channel 7 to be a predetermined diameter.
- a hydrogen-containing gas supply channel 40 is provided at the outlet of the reformer 1.
- a pressure loss regulator 41 is provided downstream from the branch point 40 a of the recycle channel 7 in the hydrogen-containing gas supply channel 40.
- the pressure loss adjuster 41 is constituted by a variable orifice capable of adjusting the pressure loss (flow rate), for example.
- the pressure loss of the pressure loss adjuster 41 is adjusted by the controller 12.
- a check valve 43 is provided in the recycle channel 7. This check valve can be omitted.
- the controller 12 makes the pressure loss of the pressure loss regulator 41 larger than the pressure loss mechanism 42 of the recycle channel 7 when enabling the flow of the hydrogen-containing gas from the upstream end to the downstream end of the recycle channel 7. Thereby, the circulation of the hydrogen-containing gas from the upstream end to the downstream end of the recycle channel 7 becomes possible.
- the pressure loss of the pressure loss regulator 41 is made substantially zero. Thereby, the circulation of the hydrogen-containing gas from the upstream end to the downstream end of the recycle channel 7 is substantially prevented.
- the check valve 43 prevents the source gas from flowing back into the hydrogen-containing gas supply path 40 through the recycle channel 7 when the source supplier 9 is stopped.
- the fourth embodiment may be applied to any one of the modification 2-5, the second embodiment, and the third embodiment.
- the fifth embodiment shows still another example of the distribution controller.
- FIG. 8 is a block diagram showing a configuration in which the open valve 8 is replaced with still another example of the flow controller in the hydrogen generator of the first embodiment as the hydrogen generator according to the fifth embodiment.
- FIG. 9 is a block diagram showing a configuration in which the open valve 8 is replaced with still another example of the flow controller in the hydrogen generator of the first modification of the first embodiment as the hydrogen generator according to the fourth embodiment. .
- description of points common to the third embodiment will be omitted, and points different from the third embodiment will be described.
- a predetermined pressure loss mechanism (flow path resistance) 42 is provided to the recycle flow path 7 as in the third embodiment.
- a switch 44 is provided downstream from the branch point 40 a of the recycle channel 7 in the hydrogen-containing gas supply channel 40. The switch 44 switches and connects the upstream portion of the hydrogen-containing gas supply flow path 40 to the short circuit 40b and the detour 40c. The short circuit 40b and the detour 40c merge at a downstream portion of the switch 44 of the hydrogen-containing gas supply flow path 40.
- a pressure loss mechanism 45 larger than the pressure loss mechanism 42 of the recycle flow path 7 is provided to the detour path 40b.
- the pressure loss mechanism 45 is applied, for example, by providing an orifice having a predetermined pressure loss (flow rate) or by designing the pipe diameter of the bypass 40b to a predetermined diameter.
- the switch 44 is constituted by, for example, a three-way valve or an open / close valve provided in each of the short circuit 40c and the bypass 40c. The switch 44 is switched by the controller 12.
- the controller 12 switches the switch 44 to the detour 40c side when enabling the flow of the hydrogen-containing gas from the upstream end to the downstream end of the recycle channel 7. Thereby, the circulation of the hydrogen-containing gas from the upstream end to the downstream end of the recycle channel 7 becomes possible.
- the switch 44 is switched to the short circuit 40b side. Thereby, the circulation of the hydrogen-containing gas from the upstream end to the downstream end of the recycle channel 7 is substantially prevented.
- the fifth embodiment may be applied to any one of the modified example 2-5, the second embodiment, and the third embodiment.
- the hydrogen generator according to the sixth embodiment is the same as the hydrogen generator according to any one of the first embodiment, the modified example 1-5, the second embodiment, and the third embodiment.
- the flow controller is controlled to allow the hydrogen-containing gas to flow.
- This configuration makes it difficult for flow path clogging due to water to condense in the third path, so that the switch is switched to the first path side and the flow control is performed while the hydrogen-containing gas is generated in the reformer.
- the possibility of problems occurring in the process that allows the hydrogen-containing gas to flow through the vessel is reduced.
- the hydrogen generator of the present embodiment may be configured in the same manner as the hydrogen generator of any of Embodiment 1, Modification 1-5, Embodiment 2, or Embodiment 3 except for the above characteristics. Good.
- FIG. 10 is a block diagram showing an example of the configuration of the hydrogen generator according to Embodiment 6.
- FIG. 10 is a block diagram showing an example of the configuration of the hydrogen generator according to Embodiment 6.
- the hydrogen generator of the present embodiment includes a temperature detector 14 that detects the temperature of the recycle channel 7.
- the other components having the same reference numerals as those in FIG. 1 are the same as those in the first embodiment, and thus detailed description thereof is omitted.
- the hydrogen generator of the present embodiment includes a detector that detects the temperature of the recycle flow path 7, this detector may directly detect the temperature of the recycle flow path 7 or indirectly detect it. May be. “Detecting directly” means detecting the temperature of the recycling flow path 7 itself. “Detecting indirectly” means detecting a physical quantity (parameter) having a correlation with the temperature of the recycle channel 7.
- the 10 includes a temperature detector 14 that detects the temperature of the recycle channel 7 and directly detects the temperature of the recycle channel 7.
- the temperature detector 14 include temperature sensors such as thermocouples and thermistors.
- the detector that detects the temperature of the recycle channel 7 is a temperature detector that detects the temperature of the heat source. It may be.
- the temperature of the second desulfurizer 3 is indirectly detected at the detected temperature of the heating source detected by the temperature detector.
- the detector that detects the temperature of the second desulfurizer 3 may be a timer that detects an elapsed time since the start of the hydrogen generator. The temperature of the second desulfurizer 3 is indirectly detected at the elapsed time measured by the timer.
- FIG. 11 is a flowchart showing an example of the operation of the hydrogen generator according to the sixth embodiment.
- the controller 12 generates the hydrogen-containing gas in the reformer 1 (step S1) before at least one of the stop of the generation of the hydrogen-containing gas and at the time of start-up. Switch to the first path 31 side (step S2). Thereafter, the controller 12 determines whether or not the detected temperature of the temperature detector 14 is equal to or higher than the temperature threshold T2, and when the detected temperature is equal to or higher than T2 (step S2A), the hydrogen-containing gas in the recycle channel 7 is determined.
- the distribution controller is controlled so as to enable distribution (step S3).
- the flow of the hydrogen-containing gas is made possible by opening the on-off valve 8 which is a flow controller.
- steps S1-S3 are executed together, the order in which steps S1-S3 are started is arbitrary. That is, all three steps may be started simultaneously, and the timing of one to three steps may be different. In the latter case, the three steps S1-S3 may be started in any order.
- Embodiment 7 is a fuel that generates electricity using the hydrogen generator of any one of Embodiment 1, Modification 1 to Modification 5 and Embodiment 2-6 and a hydrogen-containing gas supplied from the hydrogen generator. A battery.
- FIG. 12 is a block diagram showing an example of the configuration of the hydrogen generator according to Embodiment 7.
- the fuel cell system according to Embodiment 7 includes the hydrogen generator of Embodiment 1 and a fuel cell 21.
- the fuel cell 21 generates power using the hydrogen-containing gas supplied from the hydrogen generator.
- the fuel cell 21 is not particularly limited as long as it is a fuel cell. Examples of the fuel cell 21 include a polymer electrolyte fuel cell, a solid oxide fuel cell, a phosphoric acid fuel cell, and a molten carbonate fuel cell.
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Abstract
Description
実施の形態1に係る水素生成装置は、原料を用いて水素含有ガスを生成する改質器と、前記改質器に供給される原料に含まれる硫黄化合物を吸着脱硫する第1の脱硫器と、前記改質器に供給される原料に含まれる硫黄化合物を水添脱硫する第2の脱硫器と、原料が、少なくとも前記第1の脱硫器を通過し、前記改質器に供給される第1の経路と、原料が、前記第1の脱硫器及び前記第2の脱硫器のうち前記第2の脱硫器のみを通過し、前記改質器に供給される第2の経路と、前記第1の経路と前記第2の経路とを切替える切替器と、前記改質器で生成された水素含有ガスを前記第2の脱硫器に供給するための第3の経路と、前記第3の経路の上流端から下流端へ向かう水素含有ガスの流通を選択的に可能にし及び阻止する流通制御器と、水素含有ガスの生成停止前及び起動時の少なくともいずれか一方において、前記改質器で水素含有ガスを生成しながら、前記切替器を前記第1の経路側に切り替えるとともに前記流通制御器に水素含有ガスの流通を可能にさせる処理を実行するよう構成された制御器と、を備える。
図1は実施の形態1に係る水素生成装置の構成の一例を示すブロック図である。図1に示すように、本実施の形態1の水素生成装置は、改質器1と、第1の脱硫器2と、第2の脱硫器3と、分岐路4、原料流路5、切替器6と、リサイクル流路7と、流通制御器8と、原料供給器9と、制御器12とを備える。
次に、以上のように構成された水素生成装置の動作の一例を説明する。水素生成装置の動作は、制御器12の制御によって実行される。
動作例1では、水素生成装置を停止するときにおいて以下の処理を実行する。
具体的には、改質器1において、水素含有ガスの生成時には、切替器6は第2の経路32側に切り替えられるとともに流通制御器である開閉弁8が開放されて水素含有ガスの流通が可能になっている。つまり、改質器1に供給される原料は、第1の脱硫器2をバイパスして流れ、これに改質器1で生成された水素含有ガスの一部がリサイクル流路7を介して添加される。そして、この水素含有ガスが添加された原料が第2の脱硫器3に供給され、そこで水添脱硫されて改質器1に供給される。そして、水素生成装置を停止するとき、制御器12は、原料供給器9を制御して、改質器1への原料の供給を継続し、改質器1で水素含有ガスを生成するとともに開閉弁8を開放して水素含有ガスの流通を可能にした状態で切替器6を第2の経路32側から第1の経路31側に切り替える処理を実行する。
動作例2では、水素生成装置は、起動時において以下の処理を実行する。具体的には、制御器12は、起動時において、改質器1及び第2の脱硫器3を昇温する。制御器12は、改質器1が水素含有ガスの生成可能な温度になると改質器1に水蒸気を供給するとともに原料供給器9を制御して改質器1に原料を供給し、水素含有ガスの生成を開始させる。
動作例3では、制御器12は、水素生成装置の起動時には、動作例2のように水素生成装置を動作させ、水素生成動作時及び水素生成装置を停止するときには、動作例1のように水素生成装置を動作させる。これにより、第2の脱硫器3の水添脱硫触媒上に残存する未水添硫黄化合物により、問題が生じる可能性が従来よりも低減される。
図3は、実施の形態1の変形例1に係る水素生成装置の構成の一例を示すブロック図である。図3に示すように、本変形例1では、第1の経路31が、原料が第1の脱硫器2のみを通過して改質器1に供給されるよう構成されている。これ以外の構成は、実施の形態1(図1の構成)と同様である。具体的には、分岐路4の下流端が、第2の脱硫器3より下流の原料流路5において、合流点11で合流している。それ以外の図1と同様の符号を付した構成については、実施の形態1と同様であるので、詳細な説明を省略する。
変形例2の水素生成装置では、上記実施の形態1及び変形例1のいずれかの水素生成装置において、制御器は、水素生成装置の運転中において、運転時間が第1の時間閾値を経過すると、改質器で水素含有ガスを生成しながら、切替器を第1の経路側に切り替えるとともに流通制御器に水素含有ガスの流通を可能にさせる処理を実行するよう構成されている。
変形例3の水素生成装置は、変形例2の水素生成装置において、第1の時間閾値は、第2の脱硫器への累積原料供給量に応じて設定される。かかる構成により、実施の形態1に比べて、水素含有ガスの生成停止前及び起動時の少なくともいずれか一方において上記処理を実行する期間を短縮し得る。
変形例4の水素生成装置は、実施の形態1、変形例1-3のいずれかの水素生成装置において、制御器は、所定の時間以上、改質器で水素含有ガスを生成しながら、切替器を第1の経路側に切り替えるとともに流通制御器に水素含有ガスの流通を可能にさせる処理を実行するよう構成される。所定の時間は、改質器で生成された水素含有ガスを第2の脱硫器に供給して、第2の脱硫器の水添脱硫触媒上に付着している未水添硫黄化合物の水素化に必要な時間に設定される。この時間は、実験等により決定される。また、「所定の時間」を、例えば、第2の脱硫器への累積原料供給量に応じて設定してもよい。
変形例5の水素生成装置は、実施の形態1、変形例1-4のいずれかの水素生成装置において、制御器は、第2の脱硫器に設けられた水添脱硫触媒の温度が、その使用温度であるとき、切替器を第2の経路側に切り替えるよう構成されてもよい。
実施の形態2の水素生成装置は、実施の形態1、変形例1-5のいずれかの水素生成装置において、制御器は、起動時の上述の処理において、第2の脱硫器に設けられた水添脱硫触媒の温度が使用温度より低い温度であるときに、流通制御器を制御して、水素含有ガスの流通を開始させるよう構成されている。
実施の形態3の水素生成装置は、実施の形態1、変形例1-5、実施の形態2のいずれかの水素生成装置において、第2の脱硫器が使用温度よりも低い温度で原料を供給すると未水添硫黄化合物が脱離する水添脱硫触媒を備え、制御器は、起動時の前記処理において、未水添硫黄化合物が水添脱硫触媒から脱離しない上限温度以下で、流通制御器を制御して、水素含有ガスの流通を可能にするよう構成されてもよい。
実施の形態1、実施の形態2及び実施の形態3の実施例として、電気炉を備えた固定床流通反応装置に水添脱硫触媒としてCoMo系触媒10cc及びZnO系触媒5ccを設置して、水素生成装置の停止及び再起動時の挙動を模擬した実験を行った。つまり、水添脱硫触媒が第1の水添脱硫触媒である場合を模擬した。
実施の形態1、実施の形態2及び実施の形態3の実施例として、電気炉を備えた固定床流通反応装置に水添脱硫触媒としてCuZnO系触媒500ccを設置して、水素生成装置の停止及び再起動時の挙動を模擬した実験を行った。つまり、水添脱硫触媒が第3の水添脱硫触媒である場合を模擬した。
実施の形態4は、流通制御器の他の例を示したものである。
実施の形態5は、流通制御器のさらなる他の例を示したものである。
実施の形態6の水素生成装置は、実施の形態1、変形例1-5、実施の形態2、実施の形態3のいずれかの水素生成装置において、制御器は、上述の処理において、第3の経路の温度が水凝縮しない温度以上になると、流通制御器を制御して、水素含有ガスの流通を可能にするよう構成されている。
実施の形態7は、実施の形態1、変形例1-変形例5、実施の形態2-6のいずれかの水素生成装置と、水素生成装置より供給される水素含有ガスを用いて発電する燃料電池とを備える。
2 第1の脱硫器
3 第2の脱硫器
4 分岐路
5 原料流路
6 切替器
7 リサイクル流路
8 開閉弁
9 原料供給器
11 合流点
12 制御器
13 温度検知器
21 燃料電池
22 熱交換器
23 貯湯タンク
24a 第1の排熱回収経路
24b 第2の排熱回収経路
25 蓄熱量検知器
31 第1の経路
32 第2の経路
40 水素含有ガス供給流路
40a 分岐点
40b 短絡路
40c 迂回路
41 圧損調整器
42 圧損機構
43 逆止弁
44 切替器
45 圧損機構
Claims (12)
- 原料を用いて水素含有ガスを生成する改質器と、前記改質器に供給される原料に含まれる硫黄化合物を吸着脱硫する第1の脱硫器と、前記改質器に供給される原料に含まれる硫黄化合物を水添脱硫する第2の脱硫器と、原料が、少なくとも前記第1の脱硫器を通過し、前記改質器に供給される第1の経路と、原料が、前記第1の脱硫器及び前記第2の脱硫器のうち前記第2の脱硫器のみを通過し、前記改質器に供給される第2の経路と、前記第1の経路と前記第2の経路とを切替える切替器と、前記改質器で生成された水素含有ガスを前記第2の脱硫器に供給するための第3の経路と、前記第3の経路の上流端から下流端へ向かう水素含有ガスの流通を選択的に可能にし及び阻止する流通制御器と、水素含有ガスの生成停止前及び起動時の少なくともいずれか一方において、前記改質器で水素含有ガスを生成しながら、前記切替器を前記第1の経路側に切り替えるとともに前記流通制御器に水素含有ガスの流通を可能にさせる処理を実行するよう構成された制御器と、を備える、水素生成装置。
- 前記制御器は、前記処理において、前記第2の脱硫器に設けられた水添脱硫触媒の温度が、その使用温度より低い温度であるときに、前記流通制御器を制御して、前記水素含有ガスの流通を開始させるよう構成されている、請求項1記載の水素生成装置。
- 前記制御器は、前記処理において、前記第3の経路の温度が水凝縮しない温度以上になると、前記流通制御器を制御して、前記水素含有ガスの流通を開始させるよう構成されている、請求項1または2記載の水素生成装置。
- 前記制御器は、前記第2の脱硫器の温度に設けられた水添脱硫触媒が使用温度であるとき、前記切替器を前記第2の経路側に切り替えるよう構成されている、請求項1-3のいずれかに記載の水素生成装置。
- 前記制御器は、所定の時間以上、前記処理を実行するよう構成されている、請求項1-4のいずれかに記載の水素生成装置。
- 前記所定の時間は、前記第2の脱硫器への累積原料供給量に応じて設定される、請求項5記載の水素生成装置。
- 前記第2の脱硫器は、CoMo系触媒を備える、請求項1-6のいずれかに記載の水素生成装置。
- 第2の脱硫器が使用温度よりも低い温度で原料を供給すると未水添硫黄化合物が脱離する水添脱硫触媒を備え、
前記制御器は、前記処理において、前記水添脱硫触媒から脱離しない上限温度以下で、前記流通制御器を制御して、前記水素含有ガスの流通を開始させるよう構成されている、請求項1-6のいずれかに記載の水素生成装置。 - 前記水添脱硫触媒が、CoMo系触媒を備え、前記上限温度は150℃である、請求項8記載の水素生成装置。
- 前記第2の脱硫器は、CuZn系触媒を備える、請求項1-6のいずれかに記載の水素生成装置。
- 請求項1-10のいずれか1項に記載の水素生成装置と、前記水素生成装置より供給される前記水素含有ガスを用いて発電する燃料電池とを備える、燃料電池システム。
- 水素含有ガスを生成する水素生成装置の運転方法であって、
水素含有ガスの生成停止前及び起動時の少なくともいずれか一方において、
原料中の硫黄化合物を除去する第1の脱硫器を通過した原料を改質器に供給するステップと、
前記改質器で生成された水素含有ガスを、原料中の硫黄化合物を水添脱硫する第2の脱硫器に供給するステップと、
を共に実行する、水素生成装置の運転方法。
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JP2015157746A (ja) * | 2014-01-21 | 2015-09-03 | パナソニック株式会社 | 水素生成装置、燃料電池システム、およびこれらの運転方法 |
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JP2016012485A (ja) * | 2014-06-30 | 2016-01-21 | アイシン精機株式会社 | 燃料電池システム |
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US10340537B2 (en) | 2014-11-27 | 2019-07-02 | Panasonic Intellectual Property Management Co., Ltd. | Fuel cell system and control method for the same |
Also Published As
Publication number | Publication date |
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US20140072888A1 (en) | 2014-03-13 |
EP2716597B1 (en) | 2019-09-11 |
EP2716597A4 (en) | 2014-10-29 |
US9492777B2 (en) | 2016-11-15 |
EP2716597A1 (en) | 2014-04-09 |
JPWO2012164897A1 (ja) | 2015-02-23 |
JP5501528B2 (ja) | 2014-05-21 |
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